Low-lying excited states and photodissociation studies of<i>cis</i>-BrONO

Lesar, Antonija; Kovačič, Saša; Hodošček, Milan; Stadler, Margret G.; Mühlhäuser, Max; Peyerimhoff, Sigrid D.

doi:10.1080/00268970500105078

Cited by 4 publications

(6 citation statements)

References 17 publications

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“…For a reliable comparison with ClONO, we present in Table the values for BrONO calculated with the cc-pVDZ + sp basis set. We should emphasize that the energies obtained with the basis set of double-ζ quality are within about 0.1 eV of those resulting from calculations with the triple-ζ basis set …”

Section: Resultssupporting

confidence: 51%

“…We should emphasize that the energies obtained with the basis set of double-quality are within about 0.1 eV of those resulting from calculations with the triple-basis set. 9 The computed excitation energies of cis-BrONO nicely match the absorption peaks in the experimental spectrum recorded in the range of 200-365 nm. 8 The intense absorption band located at 228 nm (5.44 eV) coincides with the computed vertical energy 8 showed the low-intensity broad band centered around 290 nm (4.27 eV), which is consistent with the computed values of 4.44 eV.…”

Section: Comparison Of the Clono And Brono Low-lying Excited Statesmentioning

confidence: 52%

“…It is interesting to note the UV spectral similarity between ClONO and BrONO. The absorption spectrum of the bromine analogue has been studied by both experiment 8 and ab initio calculations, in which MRD-CI vertical excitation energies for the cc-pVTZ + sp basis set are reported. For a reliable comparison with ClONO, we present in Table the values for BrONO calculated with the cc-pVDZ + sp basis set.…”

Section: Resultsmentioning

confidence: 99%

“…The most likely UV destruction process leads to Cl + NO 2 or ClO + NO products. Finally, we present a comparison of the low-lying electronic states of ClONO to those of the bromine analogue, BrONO, just recently studied by our group …”

Section: Introductionmentioning

confidence: 99%

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Electronic Spectrum and Photodissociation of ClONO in Comparison to BrONO

et al. 2005

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A theoretical study of the low-lying singlet and triplet states of ClONO is presented. Calculations of excitation energies and oscillator strengths are reported using multireference configuration interaction, MRD-CI, methods with the cc-pVDZ + sp basis set. The calculations predict the dominant transition, 4(1)A' <-- 1(1)A', at 5.70 eV. The transition 2(1)A' <-- 1(1)A', at 4.44 eV, with much lower intensity nicely matches the experimental absorption maximum observed around 290 nm (4.27 eV). The potential energy curves for both states are found to be highly repulsive along the Cl-O coordinate implying that direct and fast dissociation to the Cl + NO2 products will occur. Photodissociation along the N-O coordinate is less likely because of barriers on the order of 0.3 eV for low-lying excited states. A comparison between the calculated electronic energies related to the two dominant excited states of ClONO and BrONO indicates that the transitions lie about 0.6 eV higher if bromine is replaced by chlorine. The stratospheric chemistry implications of ClONO and BrONO are discussed.

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Section: Resultssupporting

confidence: 51%

Section: Comparison Of the Clono And Brono Low-lying Excited Statesmentioning

confidence: 52%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electronic Spectrum and Photodissociation of ClONO in Comparison to BrONO

et al. 2005

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“…ω 5 (b 2 ) NO 2 rock ω 6 (b 1 ) op-bend 92 and cis-BrONO. 93 In each case, they utilized the MRD-CI method with basis sets up to cc-pVTZ with an additional diffuse s on N and p function on the halogen (cc-pVTZ+sp). The present work appears to be the first calculation of the electronic spectra of INO 2 , cis-IONO, and all three trans-XONO species (X = Cl, Br, I).…”

Section: Electronic Excitation Spectramentioning

confidence: 99%

An ab initio investigation of the ground and low-lying singlet and triplet electronic states of XNO2 and XONO (X = Cl, Br, and I)

Peterson

Francisco

2014

The Journal of Chemical Physics

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A systematic ab initio treatment of the nitryl halides (XNO2) and the cis- and trans- conformers of the halide nitrites (XONO), where X = Cl, Br, and I, have been carried out using highly correlated methods with sequences of correlation consistent basis sets. Equilibrium geometries and harmonic frequencies have been accurately calculated in all cases at the explicitly correlated CCSD(T)-F12b level of theory, including the effects of core-valence correlation for the former. Where experimental values are available for the equilibrium structures (ClNO2 and BrNO2), the present calculations are in excellent agreement; however, the X-O distances are slightly too long by about 0.01 Å due to missing multireference effects. Accurate predictions for the iodine species are made for the first time. The vertical electronic excitation spectra have been calculated using equation-of-motion coupled cluster methods for the low-lying singlet states and multireference configuration interaction for both singlet and triplet states. The latter also included the effects of spin-orbit coupling to provide oscillator strengths for the ground state singlet to excited triplet transitions. While for ClNO2 the transitions to excited singlet states all occur at wavelengths shorter than 310 nm, there is one longer wavelength singlet transition in BrNO2 and two in the case of INO2. The long wavelength tail in the XNO2 species is predicted to be dominated by transitions to triplet states. In addition to red-shifting from X = Cl to I, the triplet transitions also increase in oscillator strength, becoming comparable to many of the singlet transitions in the case of INO2. Hence in particular, the latter species should be very photolabile. Similar trends are observed and reported for the halogen nitrites, many of which for the first time.

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